Anthraquinone derivative and process of making same



. making further dyestuffs.

Patented May 21, 1935 UNITED/STATES PATENTKOFFICE r 2,002,264IANTHRAQUINONE DERIVATIVE: AND

PROCESS OF MAKING SAME V Hermann Bauser, Basel, 1 and Max Bommer,

Riehen, near Basel, Switzerland, assignors to the firm Society ofChemical Industry in Basle,

' Basel, Switzerland NoDrawing. -Application May 31, 1932, Serial No.614,610. In Switzerland June 29, 1931 I e 5 Claims.

This invention relates to the manufacture of new anthraquinonederivatives and their application as dyestufis. It comprises theprocessof making these derivatives as well as the derivatives themselves. i j

The invention is basedon the observation that in 1-acylamido-3halogen-anthraquinones, obtainable for example by. acylating 1-amino-3halogen-anthraquinones, the halogen may be exehanged in a surprisinglysmooth manner, with.

elimination of hydrogen halide or a salt thereof, for the most variousresidues. 7

The reaction is 'carried out by causing compounds containing at leastonereplaceable atom of hydrogen or a metal attached to nitrogen, oxygen orsulfur to react on l-acylamido-li-halogen-anthraquinones." V q Among the1-acylamido-3-halogen-anthraquinones which maybe used in the presentprocess the following may for example be mentioned: 1 formylamido 3bromanthraquinone, 1 acetylamido 3 bromanthraquinone, 1-benzoylamido-3-bromanthraquinone, 1- i' -chloro-)benzoylamido3-chloranthraquinone, l-naphthoylamido-3-chloranthraquinone,1-2-jethoxy-) naphthylamine, or the highly condensed ring systems, suchas aminoanthraquinones, aminopyranthrones, aminoanthanthronea'aminodibenzanthrones:

The reaction of. the 1-acylamide-3-halogenanthraquinones with thecompounds just named is preferably carried out in a diluent of highboiling point in presence of agents that bind acids, such as anhydroussodium acetate, potassium acetate, calcined alkali carbonates, copperoxide, magnesium oxide, and of catalysts, such as metallic copper andits compounds. The yields are generally approximately quantitative, andthe productsof thereaction are almost always obtained in crystallineformf The products obtainedin this manner may already themselves bevaluable dyestuffs, but they may also be used as intennediate productsfor The new anthraquinone derivatives obtainable according to thepresent'process yield in dyeing valuable tints of very good fastnessproperties.

For dyeing theycan also be used in the form of Itheirleuco-compounds,for instance their leucoesters- A The followingexamples illustrate the inventionythe'parts being by Weightr- I 4 KExample 1 10 parts of .1 benzoylamido-3-bromanthraquinone, obtainable bybenzoylating l-amino-3- i bromanthraquinone (compare Berichte derdeutsehen Chemischen Gesellschaft, 1916, vol. 49, page 2154), 100 partsof phenol, '10 parts of potassium carbonate and 0.2 part of copperpowder are heated together to. boiling for 4 hours, a portion of thephenol being distilled during the reaction. The mass, atlabout 80 C., isdiluted with 150 parts of alcohol; after stirring for a short time andcooling to a 50 C. the whole is filtered. The new compound of theprobable formula forms greenism yellow microscopically small tabletswhich, after severalrecrystallizations from nitrobenzene, melt at 225 C.In sulfuric acid of 96 per cent. strength the dyestuff disolves to apure red solution, whereas the parent material dissolves inthe samesolvent toga yellow orange I solution.- Thenew dyestufl obtained dyescotton from a cold vat'greenish yellow shades.

Example 2 10 parts of1-benzoylamido-3-bromanthraquinone, 56 parts ofparatoluidine, 3 parts of potassium acetate and 0.2 part of copperacetate are heated together for 24 hours in a reflux apparatus. The massgradually becomes brown, While it is at a temperature of 70 0., 150parts of alcohol are added and the mixture is stirred until theseparation of the new compound is complete. This compound ofthe-probable formula :0, i is filtered and washed first with alcoholand. then :probable formula,

Example 3 12 parts of 1benzoylamido-3- bromanthraquinone, 8' parts ofl-aminoanthraquinone, 8 parts of potassium acetate, 1 part of copperacetate and 200 parts of nitrobenzene are heated together to boiling for6 hours while stirring. The whole is filtered at C. and the solid matteris washed with nitrobenzene, then with alcohol and finally with hotwater. There: are obtained 11 partsofa red crystalline powder. Thisproduct of the dissolves to a pure blue solution in concentratedsulfuric acid or chlorosulfonic acid. When precipitated fromconcentrated sulfuric, acid solution the dyestuff dyes cotton in a coldor warm vat a strong briclrred of very good properties of fastness.

Example 4 '10 partsof I-benzoylarhido*S-bromanthraquin one, "7 parts Iof 1,4-aminomethoxyanthraquinone, 5 parts of anhydrous-sodium acetate, 1part of copper acetate and 150'parts'of 'nitrobenzene are heatedtogether to boiling for Ghours. The whole is filteredat 50 C.- andthesolidmatter Washed with nitrobenzene, alcohol a and finally with hotwater. The'new compound of the probable formula 'forms long violetneedles which dissolve to. a pure blue solution in sulfuric acid of 96per cent. strength. Introduction of this solution into water producesviolet flocks. The yield amounts to more than per cent. of that:indicated by theory. -When-precipitated: from the sulfuric acidsolution the productdyescotton in the vat bordeaux tints of very goodproperties of fastness.

Example 5 10 parts of 1-benzoylamido-3-bromanthraquinone, 9 parts ofl,5-monobenzoyldiaminoanthraquinoney5 partsof anhydrous sodium acetate,1 part of copper acetate and 150 parts of nitrobenzene areheated'together to boiling for 6 hours and the mass is worked up asdescribed in Example- 3.';There areobtained well formed small redneedles-ina yie1d of -more than per cent. of that indicated by theory.By precipitating the dyestuii of the probable formula from sulfuric'acidof 93 per cent. strength at a temperature below 5 0. there is obtained ared paste. This compound dyes cotton in a cold or Warm hydrosulfite vatstrong/brownish red tints of good properties of fastness.

When 1,8-monobenzoyldiaminoanthraquinone is used instead of the1,5-compound a similar dyestufi of the probable formula ofvery goodproperties of fastness is obtained.

. Example 6 7 10 parts of: l+benzoylamido-3-bromanthraquinone," 2.4parts of 1,5-diaminoanthraquinone, 5 parts of anhydrous sodium acetate,1 part of copper acetate and :parts'-'of: nitrobenzene are togetherheated to boiling for 6 hours as described in Example 3. The newcompound of the probable formula a a t isisolatd-by'filtration at about50 C." It is a red crystalline "powder, which after precipitation tiesof fastness. 30=

from concentrated sulfuricaacidsolution dyes cotton in the vat strongbordeaux tints of very good properties of fastness.

Example 7 .1.

A mixture of 10 parts ofIl-benzoylamido-3- bromanthraquinone, 10 ,par tsof, l,4 -monobenzoyldiaminoanthraquinone, 5 parts of potassium acetate,1 part of popper acetate and 200 parts of nitrobenzene isconverted,its-described in Examanthrimide of the ple 3, into thecorresponding probable formula The compound dyes cotton in a cold orwarm hydrosulfite vat browngred tints of good proper- Emample 8 aratedby filtering. probable formula b d the tom mic o copi yel o 1; needles;it melts at..345 C whilst darkening; Itdissolyes in sulfuric acidof 97per cent str ngth.

to a pure raspberry-red solution, wlnlstth'e parent material dissolvesin the same ,s'olyent tq an orangesolution. By-:all owingtheraspberryy VM boiling nitrobenzene whereby it is obtained in. k 'the form of veryfine small needles. After the red. solution in sulfuric acid tostand for; some time at ordinary temperature and then pouring it on ice thereisobtained anew compoundjhav ing a melting point of 298- 2991 Ql. -Whenrecrystallized from nitro-benzene it forms brown crystals; it {isapparently l-benzoylamido-B aminoanthraquinone. By hydroly zing theproducts of melting points 345 Qfand 298-299 C. with concentratedsulfuric acid at 1l0--120 C.

there is obtained 1,3-diaminoahthraquinone.

Example 9 20 parts of 1-benzoyl-amido 3-br0nianthraquinone, 7.7 parts'of thiophenol 'ortho-carboxylic acid, 10 parts of potassium carbonate"and 300* parts ot-amyl alcohol are heated toboiling for 18 hours in areflux apparatus. "After'this' op' eration the -amyl'alcohol' isexpelled byflsteam distillation, the remaining orange soluticn islil'-'- parent materialwand the probable formula I' .1; a

is precipitated by acidifying filtrate-with mineral acid. When dried? itconstitutes a crystalline redpowder. It dissolves in sulfuric acid of 97per cent. strengtnto-a, yellow solution; when the sulfuriciacid solutionis poured into water thereare precipitated red orange flakes whichdissolve to an orange solution on the addition of 'sufiicient aqueousammonia.

nimble new compound of the tered to. remove? a' small quantity ofunchanged.-

6f;- l benaoylamidobrorn anthra quinone 10 parts of.4-amino-4'echloro-zl-anthraquinonethioxanthone, 5. partsofanhydroussodium acetateyjrl part of copperacetateandv 400 parts ofnitrobenzeneare, heated to :boiling a:

for 20 hours in a reflux apparatus. The reaction product is isolated byfiltering whilst still hot and washed with nitrobenzene, then withalcohol' and. finally with hot water. The new .com- 'poundof theprobablefoi'mula 1 1 a dissolvesinsulfuric acid of lQQper cent. strengthto. a;blue solution, whilst the parent -materials ,dissolve in the samesolvent to an orange. S9111! -J- The p d m y be rec st i d I fromdyestuff has been reprecipitated from its solution in sulfuric acid of100 per "cent; strength, it dyes cotton a .cold or heated vat powerfulgrey tints.*havingvery good properties of fastness;

amino-group, such as" 5-amino-2;l anthraqub noneacridone,aminopyranthrone, ar'ninofdiben zole, there are j ob tained dyestufi'swhichidyelcot A red brown respectively.

tonyiolet-brown or black-olive ordark green or a; Example 11 17.2 artsof 1- acetylamido' tbromantliraqui L nome,"Gpartsbf1 5thaminoanthraquinone, 8 parts ofz anhydrous sodium acetate, lrpartaof:copper acetate-and 20Qrparts of: nitrobenzenesarehea-ted to boiling for18 hours in a reflux apparatus. L'Ihe whole is then allowed to coolsomewhat and is filtered to isolate the reaction" product of theprobable formula which is separated in the form of beautiful crystals.:I-Itrdissolvs in "sulfuric. acid ofn98vperz'cent.

strength .to': a'zpule' blue-solution: from which: on I pouringrintowaterrit is reprecipitatedin thelform ofblue red flakes. Theproduct.dyes. cotton'inza cold or: heated vat very fastibordeaux red. shades.

Example 1 2 i 713 :parts of Z 1-benzoyl=amido=3 chloranthraquinone, 5.5parts of 1,4;-.amin0methoxyanthraquinone, 5 parts-of. anhydrous sodiumacetate, 1

vpart of copper acetateand 150 parts of nitrobenzene are heatedtoboiling for 18 hoursin a reflux apparatus and the reaction product ofthe probable formula 1 gram of the dyestuif .made as described .inExample" 6, 5 cc. of caustic soda solution of 36 B. and 100. ccrofwaterat 25l-30. 'cparewmadeinto a paste,. 2 grams of. hydrosulfitelconc.powder are added and vatting is continued for /2 hourjatthe aboveltemperature. To. this. dye-lbath' there are added 3 cc. of. caustic sodasolution of 36 .Bhand 1 gramof hydrosulfite andthe wholeismadeup.

includingthe stock vat, to.2 litresand the stock vat is added. The goodsare entered.at'25'-30i,C. and handled for hour. There are then added 20grams of sodium chlorideor calcined sodium sulfate and dyeing iscontinued for 1 hour at 25-30-i.. .Afterrwinding oif,. thegoods. areoxi- .-dized.i or 9/; hour. in the air, rinsed :soured, rinsed.-=.and=soaped:zatthe-boil. .jOrangetintszare obtained.

What We claim is 1. As new products the anthraquinone derivatives of thegeneral formula NH-acyl *in which R represents hydrogen, alkyl, phenyl,"naphthyl or the radical of a higher condensed rin -system, whichproducts formyellow-to orange to brown to red to violet to green powderswhich dissolve in concentrated sulfuric acid to-yellow to red to bluesolutions, and vdye cottonfrom the vat yellow to red to blue to green toblack tints of very good fastnessiproperties.

2. As new products the anthraquinone derivatives of the general formula0 IIUilF-benzoyl in. which. :R represents hydrogen, alky1,:pheny1,naphthyleor: the radical of. a. higher condensed ring system, --whichproducts formiyellow-. to

orange to.brown to red-to violet to greenpowders which dissolve inconcentrated sulfuric acid to yellow to red.-to'bluesolutions'anddyeicotton from .thervat; ye1lowtto2 red to blue-to; green; to black.tints of very good fastnessproperties.

3.5As. new. products, the anthraquinone derivatives of the generalformula i NH-eB.

inwhich R represents"hydrogen; alkyl, phenyl, naphthylor theradical ofa'higher condensed "ring system, whichproducts form yellow to orange to"brown -to' red-t0 violet to green powders whichdissolve'in-concentrated sulfuric acid to yellow to "red=-to bluesolutions and-dye cotton from the vat yellowto red to blue to greentoblack tints of very good fastness properties.

4. *As new products the anthraquinonederivatives" of'the general formulain .which Rrepresents theradical of ashigher conv.densed ring system;which products form orange 5 torred tosviolet. to green powders whichdissolve in-concentrated sulfuric acid to red to blue solutionsi andzdyecotton from the vat red to blueto green -:to black ,tints of very goodfastness properties 1 5. As new products the anthraquinone derivainwhich R represents an anthraquinone radical,

tives of the general formula, whichproductsform orange to red toViolette 7 green powders which dissolve in concentrated IIULC Q sulfuricacid to red to blue solutions and dye cotton from the vat red to blue togreen to black tints 5 of very good fastness properties.

Nil-R o HERMANN HAUSER. (I) MAX BOMMER.

